Bleach-fast, fiber-reactive yellow monoazo dyes



United States Patent 3,117,958 BLEACH-FAST, FIBER-REACTIVE YELLOW MONOAZO DYES Roy Emerson Starn, In, and William Henry Gumprecht, Wilmington, DeL, assignors to E. I. du Pont de Nemours and Company, Wiimington, Del., a corporation of Delaware No Drawing. Filed Mar. 23, 1959, Ser. No. 800,031 Claims. 01. 260-153) This invention relates to bleach-fast, fiber reactive ye1-' tent No. 3,040,022, are described novel, fiber-reactive dyes of the general formula wherein R and R are benzenoid radicals bearing optional substituents, as there set forth, Z is a radical of the group consisting of CH, and C H X is a halogen atom, and Y is halogen or another substituent as there defined. These dyes produce dyeings ranging in shade from greenish yellow to yellow and characterized by outstanding fastness to bleach, even at chlorine concentrations of 0.3

We have now found that bleach-fast dyes of a redder shade of yellow and having greater tinctorial strength are obtained if the R radical in the above general formula is replaced by the p,p'-radical of o,o'-disuifo-stilbene. In other words, the novel fiber-reactive dyes of this invention are expressed by the general formula wherein n is 1 to 3; M is an alkali-metal; Q is a nonionic substituent of the group H, Cl, alkyl, O-alkyl; Z is CH or C H X is C1 or Br; and Y is Cl, Br, O-alkyl, S-alkyl, NH monoalkylamino, dialkylamino, monoalkanolamino, dialkanolamino, arylamino, N-alkyl-arylamino, and arylamino radicals bearing water-solubilizing groups, the alkyls and alkanols in these definitions of Q and Y being radicals of l to 4 C-atoms, and the aryls in the definition of Y having not more than C-atoms in their cyclic structure.

It will be noted that the novel dyes of this invention possess the foilowing characteristics in their structure: They are monoazo dyes, having a triazine radical which bears at least one halogen atom (Cl or Br); they possess a 1,2-naphthotriazole radical; one of the 'N-atoms of the triazole ring is attached to a 2,2-disul-io-stilbene radical; the second component of the azo dye is a benzenoid 3,117,958 Patented Jan. 14, 1964 "ice ring; the triazine ring is attached to said benzenoid component by means of a secondary amine radical; the entire molecule contains at least 3 and up to 6 or 7 sulfo groups, of which at least one is located in the naphthalene nucleus, and the dye chromophore, that is, the dye molecule exclusive of .the triazine ring and its substituents, is free of OH and NH groups.

In addition to possessing outstanding fastness to bleach, the dyeings produced by our novel dyes possess other desirable qualities, such as good fastness to light and good fastness to after-treatment with textile-finishing resins '(such as crease-proofing or fiber-setting resins).

Generally speaking, our novel compounds are synthesized by preparing first, in conventional manner, an amino-stilbene-naphthotriazole compound of the formula wherein M is an alkali-metal and n is an integer from 1 to 3. See, for instance, U.S.P. 2,029,591. This compound is then diazotized and coupled to a secondary arylamine of the formula wherein Q and Z are as above defined, and the aminoazo dye thus obtained is then condensed with a dihalogenoor tri-halogeno-triazine compound of the formula N X-C/ O-X i t C i wherein X and Y are defined as above.

CX It i it When Y is halogen, the said condensation is eiiected at ice temperatures (0 to 5 C.) in aqueous medium, whereby the resulting end product possesses two halogen atoms on the triazine ring. But if the reactive dye is to contain onlyone halogen in the 'tr-iazine ring, either one of two routes may be resorted to: (a) reaction of the aminoazo compound, mole per mole, with a cyanuric halide, followed by reaction with one mole of acornpound which forms a Y group other than halogen, or ('b first reacting a compound of the latter group, mole per mole, with a cyanuric halide, followed by reaction with one mole of the aminoazo dye. In either route,-the reaction with cyanuric-halide is eilected at ice temperatures (0 to 5 C.) in aqueous medium, and the second halogen atom on the 'triazine ring is reacted at a temperature in the range of 10 to 70C., likewise in aqueous medium.

amine, an N-alkylaarylamine, or an arylor N-alkylarylhowever, be also recovered, in known manner, in the 3 4 The compoundswhich are employed to form the Y a 40 parts of 2 N sodium carbonate were added, to maingroup other than halogen are, for instance, a lower altain the pH at 4 to 6. The resultant solution of primary cohol (1 to 4 C-atoms), a lower mercaptan, a monocondensation product of sodium metanilate and cyanuric alkylamine, a dialkylamine, an alkanolamine, an aryl chloride was added to one portion of the slurry of the methylamino compound (H), which had previously been amine bearing from 1 to 3 water-solubilizing groups (eg adjusted to pH 6.5 and heated to 50 to 55 C. 2 N so- SO H or COOH). dium carbonate was added, as needed, to maintain the The final dye is generally salted out with common pH at 4 to 6 until the pH remained constant for min salt; hence its sulfo groups have the form SO Na. It may, utes. The slurry was then adjusted to pH 6.5 at 50 to 55 C., and suflicient NaCl was added to produce a 10% form of a potassium or lithium salt, or it may be con- 10 NaCl solution by volume. The product was filtered otf verted into one or the other of these salts, in known and dried. The isolated product is a reactive dye, and is manner, after isolation in the form of sodium salt. believed to have the structure on; N\ t C W I 1 N N =N SOBNfi soiNa in;

sOaNa SO Na Without limiting this invention, the following exam- It is a brown powder, which dissolves in water to give a p les are given to llustrate our preferred mode of operayellow solution. When applied to cotton broadcloth from tron. Parts mentioned are by weight. an aqueous bath by the method described in Example 7 hereinbelow, it exhibits a bright yellow shade having excellent light and wash fastness, and having outstanding A quantity of the trisodium salt of an amlno-stllbene f t to chlorine bleach and Peroxide compound of the formula Example 1 Example 2 A solution was prepared by dissolving 39.7 parts 2- j l amino-p-benzenedisulfonic acid in 260 parts of water and :N SONa sOiNa adjusting the pH to 6.5. To this solution at 0 to 5 C.

was added 27.6 parts of cyanuric chloride in 122. parts of acetone. parts of 2 N sodium carbonate were added,

- as needed, to maintain the pH at 4 to 6. The resultant SQINa (1) solution of primary condensation product of Z-amino-pwas prepared in the conventional manner (see, for inbenzenedisulfonic acid and cyanuric chloride was added stance Example 3 of U.S.P. 2,029,591), using sodium to the remaining portion of the slurry of the methylamino hypochlorite in strongly alkalinesolution for oxidation 40 compound (II), of Example I which had previously been to the triazole (see, for instance, Example 1 of U.S.P. adjusted to pH 6.6 and heated to to C. The remainder of the procedure was as in Example 1, and the To a solution of 133.8 parts .of said amino-stilbene isolated product is believed to have the structure:

I H O it i l N N SOaNa SOaNa NaOaIS v C/ SO aN SOaNa compound (I) and 15.2 parts of sodium nitrite in 2,000 It is a yellow-brown powder, which gives a shade on parts of water at pH 7 and at 0 to 5 C., was added cotton very similar to that obtained from the dye of Exparts of 10 N hydrochloric acid. After stirring for one ample 1.

hour at 0 to 5 C. the excess nitrous acid was removed 0 Exam le 3 with sulfamic acid. To the resulting diazonium slurry, p

21.9 parts of N-methy1aniline were added; the mass Was 28.0 parts of N-ethyl-m-toluidine were added to an stirred at 0 to 5 C. for one hour; its pH was adjusted aqueous slurry of the diazonium compound obtained from to 2.5 with 10 N NaOH, and the mixture was further 60 the amino-stilbene compound (I), obtained as in Exstirred overnight at room temperature. The resulting ample 1, and the mass was stirred at 0 to 5 C. for one slurry, containing the azo compound of Formula 11, hour, adjusted to pH 2 with 10 N NaOH, and stirred over-'- lfiI-NQCH=CHON=NONHOE IL SO3N8 S|O3NB v I SOaNa (II) was divided into two equal portions. night at room temperature. The pH of the resulting A solution was prepared by dissolving 30.8 parts of soslurry was adjusted to 6.5, and the mass was heated to dium metanilate in 300 parts of water and adjusting the 50 to 55 C. pH to 6.5. To this solution at 0 to 5 C. was added A column of the primary condensation product o b- 27.6 parts of cyanuric chloride in 122 parts of acetone. tained as in Example 1 from 70.2 parts of sodium metanilate and 64.2 parts of cyanuric chloride, was then added, in lieu of the aniline there mentioned, 21.4 parts of diand 2 N sodium carbonate was added, as needed, to mainethanolamine are added here, over a 1 hour period. The tain the pH at 4 to 6 until the pH remained constant for rest of the procedure is as in Example 5, and the recovered minutes. The slurry was then adjusted to pH 6.5 at product has similar dyeing qualities.

50 to 55 C., and sufficient NaCl was added to produce In a similar manner, the dichlorotriazine compound of a 10% NaCl solution by volume. The product was fil- 'Formula I'II maybe reacted with ammonia,ethanolamine,

tered off and dried. The isolated product, which is bea lower monoalkyl amine, e.g. methyl, ethyl, butyl or 3- lieved to have the structure methoxypropylamine, a lower alcohol, e.g.-methyl, ethyl p (llz s /N\ ILI -NQCH=CH N=NC NC 0-01 I I It i: -N SO Na some CH: Aw

sozNtl SOQNS.

is a brown powder which gives a similar shade on cotor butyl alcohol, or an alkyl mercaptan, e.'g. ethyl or ton and possesses similar fastness properties as the dye propyl mercaptan, to replace one of the chlorine atoms of Example 1. with the corresponding NH NH-alkanol, -NH- Example 4 alkyl, O-alkyl or S-alkyl group, respectively.

The procedure of Example 1 is repeated except that Example Procedure A the resulting aqueous slurry of the methylamino compound of Formula II is here treated with 37 parts of A 4.15% aqueous solution of the reactive dye of Excyanuric chloride at 0 to 5 C. There is obtained a ample l, for instance, is padded on cotton broadcloth at reactive dye of the probable structure 70 C. to a weight increase of 60% on the fabric. After on. N r l p: N- CH=CH N=N N(I3 (F431 1 N N :N SOaNEi soiNa S03Na (III) When applied .to cotton broadcloth from an aqueous bath drying, the fabric is repadded in the same manner with a by the method described in Example 8 hereinbelow, it solution which contains 25% sodium chloride and 1.2% exhibits a shade and fastness properties similar to those sodium hydroxide. The wet fabric'is steamed for two of the dye of Example 1. minutes and then scoured at the boil for two minutes with a solution containing 0.3% sodium carbonate and 0.2% of the condensation product of 20 moles of ethylene 196 P 0f the dichlorom'azine dye Obtained in oxide with one mole of a C alcohol. The fabric is then ample 4 (Formula 111), are dissolved in 2000 parts of i d d d i d water, and 18.9 parts of aniline are added while maintaining the pH at 4 to 6 with 2 N sodium carbonate. The

Example 5 Example 8.Dyeing Procedure B reaction mass is stirred at 20 to 25 C. for 3 hours. The The dichlorotriazine dye of Example 4 (Formula III) resulting condensation product of formula is applied to cotton broadcloth in exactly the same man- N N- CH=CH N=N-NC 0-01 u l 1 u I t N N N SOgNn SOsNa \C S OgNZl is salted out, filtered off, and dried. When applied .to ner .as described in Example 7, except that the dye solucotton broadcloth by the procedure of Example 7 below, v tion is padded at room temperature (20 to 25 (1.). The

it produces dyeings of similar shade and fastness qualities subsequent repadding, steaming, scouring, etc., are done as the product of Example 1. in the same manner as in Example 7.

In a similar manner, the dichlorotriazine dye of EX- It will be understood that the details of the above inarnple 4 may be reacted with other arylamines and N- vention may be varied widely without departing from alkylal'ylamines, The 111', 0T P-tohlidines the spirit of this invention. Thus, in the preparation of yl (or N-ethyUtOluidines, to replace one of the chlorine the amin0 sti1ben compound (I) i Example 1 h 4- atoms With the coffesPonding Y y amino-l-naphthalene-sulfonic acid may be replaced by W P- other ortho-coupling aminonaphthalene-sulfonic acids, for

Example 6 instance, 6-amino-2-naphthalene-sulfonic acid, 8-amino-1,-

The procedure of Example 5 is repeated except that S-naphthalene-disulfonic acid and its 8,2,5 and 8,3,5 isomers; 7-amino-1,3-naphthalene-disulfonic acid and its 7,- l,5 isomer; or S-amino-1,3,6-naphthalene-trisulfonic acid.

Likewise, in Example 1, the 21.9 parts of N-methylaniline may be replaced by 27.4 parts of N-methyl-2,5- xylidine or by the equivalent amounts, respectively, of N- methyl-o-toluidine, N-methyl-o-chloroaniline, N-methylo-anisidine or the corresponding meta compounds.

In the primary condensation products of cyanuric chloride with sodium metanilate (Examples 1 and 3) or Z-amino-p-benzenedisulfonic acid (Example 2) the named aromatic amines may be replaced by equivalent quantities of aniline; toluidine; chloraniline; aniline derivatives containing sulfo or carboxy groups in any of the o, m, or p positions; 1-amino-4-naphthalene-sulfonic acid; l-amino- 4,8-naphthalene-disulfonic acid; and the like.

It will be noted that according to this invention the initial aminostilbene-naphthotriazole compound may be so chosen as to have from 3 to 5 sulfo groups in its structure. The substituent Y on the triazine ring may also possess a plurality of sulfo or carboxy groups. It is recommended, however, to choose Y so that the final dye shall contain no more than 7 such solubilizing groups.

It will be clear at this point that our invention provides novel dyes having valuable practical properties. Thus- The novel dyes of this invention are useful as reactive dyes for materials possessing exchangeable hydrogen atoms, e.g., textile fibers especial-1y celluosic fibers, wool, silk, nylon and similar materials, including paper, leather, plastic film, etc., which contain radicals such as OH, ONa or NH The new reactive dyes are yellow in shade and are characterized particularly by high tinctorial strength and SOsM wherein n is a numeral from 1 to 3, M is an alkali metal, Q is a non-ionic substituent of the group consisting of H, Cl, alkyl and O-alky-l, the alkyls being radicals of 1 to 4 C-atoms; Z is a radical of the group consisting of methyl and ethyl; X is a halogen atom of the group consisting of Cl and Br; Y is a member of the group consisting of Cl, Br, O-alkyl, S-alkyl, primary amino, monoalkylamino, dialkylamino, monoalkanolamino, dialkanolamino, arylamino, N-alkyl-arylamino, and arylamino and N-alkylarylamino radicals bearing water-solubilizing groups, the alkyls and alk-anols aforementioned being radicals of 1 to 4 C-atoms each and the aryls being aromatic radicals of not more than 10 C-atoms in their cyclic structure.

2. A compound as in claim 1, wherein Y is an aromatic substituent having not more than 10 C-atoms in its cyclic SOaNa SO Na uaoa s soaNa References Cited in the file of this patent UNITED STATES PATENTS 1,667,312 Fritzsche et a1 Apr. 24, 1928 2,696,486 Gunst Dec. 7, 1954 2,795,576 Fasciati June 11, 1957 2,795,577 Feemau June 11, 1957 2,860,129 Gunst Nov. 11, 1958 2,873,269 Fasciati et a1 Feb. 10, 1959 2,951,071 Tilley Aug. 30, 1960 2,951,072 Tilley et al Aug. 30, 1960 OTHER 'REFERENCES Gilman: Organic Chemistry, volume III, pages 293- 

1. A COMPOUND OF THE FORMULA 